UA124040C2 - OXYGEN ABSORBING PLASTIC MATERIAL - Google Patents

Abstract

The invention relates to a polyether-polyester copolymer comprising: (i) polyether segments wherein at least one polyether segment contains at least one polytetramethylene oxide segment, (ii) polyester segments, (iii) bridging elements of the structure-CO-R2-CO-, wherein R2 represents an optionally substituted bivalent hydrocarbon residue consisting of 1 to 100 carbon atoms; (iv) one or two end-caps R1-O-(C2-C4-O-)e-*, wherein R1 is an optionally substituted hydrocarbon residue and e is an integer of from 0 to 1000.

Description

The field of technology to which the invention belongs

The present invention relates to a simple polyester-polyether copolymer with a terminal group, which is capable of absorbing oxygen, and its use in compositions and products capable of removing oxygen or functioning as an active oxygen barrier.

Technical level

Thermoplastic resins such as PET (Polyethylene Terephthalate) are widely used to produce several types of packaging and storage containers. PET is mainly used in the beverage industry because it is transparent like glass, but much lighter; it is also resistant to cracking; fully recyclable and has the appropriate color variability and different designs of PET bottles are possible. The biggest disadvantage of PET is its permeability to gases and, in this case, especially its permeability to oxygen.

It is well known that the packaging of electronics, personal hygiene items, household, industrial, food and beverage products requires high barrier properties in relation to oxygen to preserve the freshness and quality of the contents of the package. In particular, for sauces and beverages such as juices, beer and tea, packaging material with high barrier properties or the ability to block the penetration of oxygen and/or remove the oxygen that has entered is required to avoid oxidation of the products and extend the shelf life of the products .

A number of strategies have been used to overcome these limitations and increase the shelf life of oxygen-sensitive products (beer, juice or tomato sauce). In the packaging industry, for example, multilayer structures containing mixed polymer layers have been developed. These multi-layer packaging containers have improved barrier properties, close but not comparable to those of glass and steel, while losing many of the recycling advantages of single-layer containers such as PET, polyethylene naphthalate (PEN) or polyolefin bottles. In addition, the transparency of the container is often significantly reduced. Maintaining the right balance of recyclability, barrier properties and transparency is most important for bottling applications.

The use of multi-layered bottles, which contain an inner, sometimes with alternating layers, layer of polymer material with higher barrier properties compared to

With outer polymer layers, is a common phenomenon. Usually, the central layer is a polymer with high barrier properties, which slows down the penetration of oxygen through the wall of the container. Examples of such passive polymers with high barrier properties include ethylene vinyl alcohol (EMON) and polyamides, preferably a partially aromatic polyamide containing metaxylylene groups such as poly(m-xylylene dipamide),

MHob. A common structure for such multilayer structures will include an inner and outer layer of PET with a central layer of polyamide or an inner and outer layer of polyolefin with a central layer of ethylene vinyl alcohol (EMON) polymer.

Another strategy that can also be combined with the use of passive barriers is the use of an active oxygen scavenger to reduce or eliminate oxygen inside the package. The method of providing barrier properties in relation to oxygen, when a substance absorbs or reacts with oxygen, is known as a reactive oxygen barrier and differs from passive oxygen barriers, which try to hermetically isolate the product from oxygen as a passive approach. Several oxygen scavenging systems are known in the art, among others, oxygen scavenging compositions comprising an oxidizable substituted or unsubstituted ethylene unsaturated hydrocarbon and a transition metal catalyst are well known effective solutions.

Containers such as sachets filled with oxygen scavenging compositions are well known examples of applications of such materials. However, these applications are generally limited to solids and solid foods, and require special care to avoid ingestion.

To solve this problem, oxygen absorbers have also been incorporated into the polymer resin that forms at least one layer of the container, and small amounts of transition metal salts can be added to catalyze and actively enhance the oxidation of the absorbers, improving the barrier characteristics of the container. This method makes it possible to eliminate or reduce the supply of oxygen from the outside, as well as unwanted oxygen from the packaging cavity, which could accidentally enter during packaging or filling.

Modified polyesters are also widely used as oxygen absorbers.

It was established that various modifications of esters are active oxygen absorbers. IN

О5б6О083585А, MO 98/12127 and UMO 98/12244 disclosed polyester compositions that absorb 60 oxygen, and in which the absorbing component is polybutadiene.

Other modifications consist in the introduction of ether groups using, for example, poly(alkylene oxide)s. 6455620 discloses a poly(alkylene glycol) that acts as an oxygen scavenger mixed with various thermoplastic polymers. 5 UMO 01/10947 also discloses oxygen scavenging compositions containing an oxidation catalyst and at least one simple polyester selected from the group consisting of poly(alkylene glycols), copolymers of poly(alkylene glycols) and mixtures containing poly (alkylene glycol) and, suitable for inclusion in products, and which contain oxygen-sensitive products.

UMO 2009/032560A1 discloses oxygen scavenging compositions that contain an oxidation catalyst and a complex ether copolyester that includes segments of the ether that include poly(tetramethylene-coalkylene ether) that has a low level of turbidity.

MO 2005/059019 A1 and UMO 2005/059020 A2 disclose a composition that includes a copolymer that includes segments of polypropylene oxide and a polymer with improved properties of an active oxygen barrier compared to previously known compositions.

The above-mentioned oxygen absorption systems are aimed at reducing the oxygen content in the package to the minimum possible level. However, this is not always desirable. Not all products have the same requirements for the appropriate atmosphere to extend their shelf life. In the case of wine, fruits and vegetables, it is desirable to create an appropriate atmosphere, with a limited oxygen content, to ensure a pleasant taste. In the case of meat and fish, the oxygen content of the atmosphere is necessary to avoid the growth of some pathogenic anaerobic bacteria, such as Siovigidicht roichipitus.

In order to maintain a certain low oxygen content in the package, it is necessary to match the supply of oxygen to the package with the rate of oxygen uptake by the oxygen scavenging composition. This can potentially be achieved by reducing the oxygen scavenging content of the packaging composition. However, this would come at the expense of the package's overall ability to absorb oxygen, thereby reducing the shelf life of the product contained within the product.

Therefore, it is desirable to create an oxygen scavenging system that is able to precisely control the rate of the oxygen scavenging reaction to the desired reduced level and maintain this level throughout the intended shelf life of the product, thus providing a high removal capacity.

It has unexpectedly been found that certain polyester-polyester copolymers, as described below, can be effectively used to effect and control oxygen absorption in a thermoplastic material.

Brief summary of the essence of the invention

The subject of the present invention is a copolymer of simple polyester-complex polyester, which includes () segments of simple polyester, and at least one segment of simple polyester contains at least one segment of polytetramethylene oxide, (i) segments of complex polyester, (ii) bridging elements of the -СО structure -H2-СО-, where K2 represents an optionally substituted divalent hydrocarbon residue consisting of 1-100 carbon atoms, and the substituents are preferably C:i-Cv-alkoxy, nitro, cyano or sulfo or their combination; (m) one or two terminal groups K1-O-(C2-C4-O-)e--, where K1 represents an optionally substituted hydrocarbon residue and e represents an integer from 0 to 1000.

The polyether-polyether copolymer according to the invention is preferably an unbranched copolymer, but it can also contain small amounts, i.e. up to 1095 mol., of trifunctional or tetrafunctional comonomers, such as trimellitic anhydride, trimethylpropane, pyromellitic dianhydride, pentaerythritol and other polyacids or polyols , known in this field of technology.

In addition to the polytetramethylene oxide segments, the polyester(s) segments may contain other alkylene oxide segments, such as ethylene oxide, propylene oxide, or a combination thereof.

Preferred implementations of segments of simple polyester (i) are represented, for example, by formulas (I), (Ia), (IB) and (Ic) and optionally (I) below: (9) | (c) (c) relay I (I) in which

K represents an integer 0-70, preferably 0-35, more preferably 0-30; m represents an integer 0-250, preferably 0-125, more preferably 0-50; x represents an integer 0-250, preferably 0-125, more preferably 0-12;

y represents an integer 0-250, preferably 0-125, more preferably 0-50; 7 represents an integer of 0-250, preferably 0-125, more preferably 0-12; and the sum of Kemzhkhnut: is 0-1070, mostly 0-535.

For мхх»2 and for m and хХО, and for у;»2 and у and 7270, the obtained part of polyethylene oxide/polypropylene oxide copolymer can represent a randomly distributed copolymer or a block copolymer in which both blocks (polyethylene oxide block or polypropylene oxide block) can be chemically bound to the polytetramethylene oxide block.

Formula (Ia) sv, sut sn kayak Ya kna Art titer er acne plate (a) in which p represents an integer 0-35, preferably 0-20, more preferably 0-15; m represents an integer 0-35, preferably 0-20, more preferably 0-15; d represents an integer 0-250, preferably 0-125, more preferably 0-50; r is an integer 0-250, preferably 0-125, more preferably 0-12; and the sum of rim/njg is 0-570, preferably 0-290.

For dyag"2 and for 4 and 20, the resulting part of the polyethylene oxide/polypropylene oxide copolymer can be a randomly distributed copolymer or a block copolymer.

Formula (IB)

SN. networks

SN. (Iv) in which

K - represents an integer 0-250, preferably 0-125, more preferably 0-12;

And - represents an integer 0-35, preferably 0-20, more preferably 0-15;

M - represents an integer 0-250, preferably 0-125, more, preferably 0-50;

M - integer 0-35, preferably 0-20, more preferably 0-15;

O represents an integer of 0-250, preferably 0-125, more preferably 0-12; in addition,

Y4M cannot be chosen equal to 0; and the sum of Ka «MM is 1-820, preferably 2-415.

In the case where Ki »2 and K, Y and MO, or in the case where MO»2 and M, O, M20, the obtained part of the polypropylene oxide/polytetramethylene oxide copolymer may represent a randomly distributed copolymer or a block copolymer in which both blocks (polypropylene oxide block

Zo or the polytetramethylene oxide block) can be chemically bonded to the polyethylene oxide block.

Formula (Is) sn, (Is) in which

P - represents an integer 0-250, preferably 0-125, more preferably 0-50;

O - represents an integer 0-35, preferably 0-20, more preferably 0-15;

B - represents an integer 0-250, preferably 0-125, more preferably, 0-12; 5 - represents an integer 0-35, preferably 0-20, more preferably, 0-15;

T - represents an integer 0-250, preferably 0-125, more preferably, 0-50; in addition, 0-5 cannot be chosen equal to 0; and the sum of Rab is 1-820, preferably 2-415.

In the case where РеО»2 for both P, 0 and 20, or for the case where 5122 and 5, T and KO, the resulting part of the polyethylene oxide/polytetramethylene oxide copolymer may represent a random copolymer or a block copolymer, with both blocks (polyethylene oxide block or polytetramethylene oxide block) can be chemically bonded to the polypropylene oxide block.

Formula (Id) software in that tt in which

M - represents an integer 0-250, preferably 0-125, more preferably 0-50;

M - represents an integer 0-250, preferably 0-125, more preferably 0-12;

MU - represents an integer 0-70, preferably 0-35, more preferably 0-30; and the sum of Ozh-Mzhuu is 3-570, mostly 5-285. In this embodiment, the polyester segment may be a homopolymer, a random copolymer, or a block copolymer.

In all formulas, the asterisk " represents a connection with a bridging element (its).

Predominantly, segments of simple polyester (ii) are represented by the formula (I): ,

K2 and KZ, independently of each other, represent an optionally substituted hydrocarbon residue consisting of 1-100 carbon atoms, in which the substituents are mainly C1-C5- alkoxy, nitro, cyano and sulfo. and represents an integer 1-50, preferably 1-30, in particular 1-25.

Preferably, KZ and KZ independently of each other represent an aliphatic hydrocarbon residue with 1-24 carbon atoms, an olefinic hydrocarbon residue with 2-24 carbon atoms, or an aromatic hydrocarbon residue with 5-14 carbon atoms, where the specified hydrocarbon residues are optionally substituted with C-C5 -Alkoxy, nitro, cyano or their combination.

In a preferred embodiment, K2 and KZ represent an aliphatic hydrocarbon residue consisting of 2-18 carbon atoms, and most preferably, consisting of 2-6 carbon atoms.

An aliphatic hydrocarbon residue can be linear, branched or cyclic. In addition, the aliphatic hydrocarbon residue may be saturated or unsaturated. Mostly it is saturated.

Preferred aliphatic residues are ethylene, 1,2-propylene, 1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,4-butylene, 2,3-butylene, 1,5-pentylene, 1, 6 hexamethylene, 1,7-heptamethylene, 1,8-octamethylene and 1,4-cyclohexylene and their mixtures. Particularly preferred residues are ethylene, 1,2-propylene, 1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,4-butylene, 2,3-butylene and 1,6-hexamethylene and their mixtures . The most preferred residues are ethylene, 1,2-propylene and 1,4-butylene and their mixtures.

In the next preferred embodiment, K2 represents an aromatic system. Aromatic

A system can be mono- or polycyclic, such as di- or tricyclic. Preferably, the aromatic system consists of 5-25 atoms, and even preferably more than 5-10 atoms.

The aromatic system is mainly formed by carbon atoms. In an additional embodiment, it consists in addition to carbon atoms of one or more heteroatoms, such as nitrogen, oxygen and/or sulfur. Examples of such aromatic systems are benzene, naphthalene, indole, phenanthrene, pyridine, furan, pyrrole, thiophene, and thiazole.

The preferred elements of the aromatic structure for K2 are 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,8-naphthylene, 1,4-naphthylene, 2,2-biphenyene, 4,4-biphenyene, 1, 3-phenylene-5-sulfonate, 2,5-furanilene and their mixtures.

Particularly preferred structural elements for K2 are ethylene, 1,2-propylene, 1,3-propylene, 2,2-dimethyl-1,3-propylene, 1,4-butylene, 2,3-butylene, 1,6-hexamethylene, 1,4-cyclohexylene, 1,3-phenylene, 1,4-phenylene, 1,8-naphthylene and their mixtures. The most preferred structural elements for Ka are 1,3-phenylene, 1,4-phenylene and their mixtures.

In another preferred implementation, the short circuit can be represented by the formula (Pa):

Y fot (c) (Pa) where 72 can be an integer 0-100.

Bridging elements (ii) can connect segments of simple polyester (ii), segments of complex polyester (ii) and/or end groups (im). Bridging elements are described by formula (I):

And dev (11): where K2 denotes the values given above. (im) end groups are connected to the bridging element (ii). The connection is marked with an asterisk 7.

Preferred end groups can be described by the following general formula

B1-0-(C2-C4-O-)e-7, where K! represents an aliphatic hydrocarbon residue with 1-24 carbon atoms, an olefinic hydrocarbon residue with 2-24 carbon atoms, an aromatic hydrocarbon residue with 6-14 carbon atoms, and the specified hydrocarbon residues are optionally substituted by C-C5-alkoxy, nitro, cyano, sulfo or combinations thereof, and e represents an integer 0-1000, preferably an integer 0-500 and most preferably an integer 0-150.

In a preferred embodiment, K1 is an aliphatic hydrocarbon residue consisting of 1-18 carbon atoms and more preferably consisting of 1-12 carbon atoms. An aliphatic hydrocarbon residue can be linear, branched or cyclic. In addition, the hydrocarbon residue can be saturated or unsaturated. Mostly it is saturated.

Particularly preferred aliphatic residues for KI are methyl, ethyl, p-propyl, isopropyl, p-butyl, isobutyl, t-butyl, tert-butyl, p-pentyl, isopentyl, t-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, p -hexyl, utorhexyl, p-heptyl, p-octyl, 2-ethylhexyl, p-nonyl, p-decyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, methyl phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl.

The most preferred residues are methyl, ethyl and p-dodecyl. The most preferred residue is methyl.

In the additional preferred implementation of CC! can be represented by an aromatic system. The aromatic system can be mono- or polycyclic, such as di- or tricyclic. Preferably, the aromatic system consists of 6-14 carbon atoms, more preferably 6-10 atoms.

The aromatic system is mainly formed by carbon atoms. In an additional embodiment, it consists in addition to carbon atoms of one or more heteroatoms, such as nitrogen, oxygen and/or sulfur. Examples of such aromatic systems are benzene, naphthalene, indole, phenanthrene, pyridine, furan, pyrrole, thiophene, and thiazole. In addition, the aromatic system can be chemically linked to one, two, three or more of the same or different functional groups. Suitable functional groups are, for example, alkyl alkenyl, alkoxy-, poly(alkyloxy), cyano- and/or nitro functional groups. These functional groups can be in any position of the aromatic system.

Particularly preferred groups K1-O-(C2-C4-O-)e-7 correspond to the following formulas vi o-ia 5 o-i-» sn, sn.

K1 OT a (in) 2.7 sn, thread To i 1 Os a Oo-x»-

K1 Os b (F) and sn. re; Art ОЙ oo

KI O7a with Oo-r sn, 204 dr tto

E1 Oo7j s (o); or sn, where different monomers are distributed randomly, in blocks or a combination of random and block distribution

B can be selected as an integer 0-250, preferably 0-125, more preferably 0-50 and can be selected as an integer 0-250, preferably 0-125, more preferably 0-12; c can be selected as an integer 0-70, preferably 0-35, more preferably 0-30, and the sum of the digits is 0-570; and K1 is as defined above.

The number average molecular weight of the copolymers according to this invention is preferably 2000-1000000 g/mol, more preferably 3500-100000 g/mol, most preferably 5000-50000 g/mol.

The mass ratio o, defined as the mass ratio between the content of poly(tetramethylene oxide) and the total content of all dicarbonyl elements of the structure, i.e. in (ii) and (ii), copolymers according to the present invention is preferably 0.1-10, preferably exceeds 0.2- 5 and even more preferably 0.5-2.

The mass ratio c, defined as the mass ratio of the content of the terminal group to the total content of all dicarbonyl elements of the structure, i.e. in (ii) and (ii), of the copolymers according to this invention, is preferably 0.001-100, more preferably 0.005-50 and most preferably 0, 01-2.

Copolymers according to the present invention can be obtained by polycondensation of at least one segment of a simple polyester, which includes at least one segment of polytetramethylene oxide, at least one segment of a complex polyester, at least one bridging element and at least one end group K1-O-(C2 -C4-O-)e-7.

The starting compounds, which provide segments of the simple polyester(s) according to the invention, can be homo- or copolymers, the copolymers can be block, statistical or segmented. Examples of starting compounds are: poly(tetrahydrofuran)-diol, poly(propylene glycol)-diol, poly(ethylene glycol)-diol, poly(ethylene glycol)-co-poly(propylene glycol)-diol, poly(ethylene glycol)-copoly(tetrahydrofuran)- diol, poly(propylene glycol)-co-poly(tetrahydrofuran)-diol and poly(ethylene glycol)-co-poly(propylene glycol)-co-poly(tetrahydrofuran)-diol.

The polyester segment can be synthesized directly during the polycondensation reaction or introduced as a pre-synthesized building block at the beginning of the reaction. Preferred segments of simple polyester are those resulting from the condensation reaction of dibasic acids or their esters or anhydrides, and diols.

Examples of starting compounds that form segments of simple polyesters (ii) according to the invention are dimethyl terephthalate, terephthalic acid, dimethyl isophthalate, isophthalic acid, dimethyl adipinate, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,2-cyclohexane-dicarboxylic acid, dimethyl ether of 1,4-cyclohexanedicarboxylic acid and ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 2,2-dimethyl-1,3-propanediol, 1 ,6-hexanediol, diethylene glycol, triethylene glycol, poly(ethylene terephthalate) and poly(butylene terephthalate).

Examples of starting compounds that form bridging elements (ii) according to the invention are dimethyl terephthalate, terephthalic acid, dimethyl isophthalate, isophthalic acid, dimethyl adipinate, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, 1,2-cyclohexane-dicarboxylic acid, dimethyl ether 1,4-cyclohexane-dicarboxylic acid.

Examples of starting compounds that form end groups are monomethoxylated poly(ethylene glycol)-monool, monomethoxylated poly(ethylene glycol)-co-poly(propylene glycol monool, lauryl alcohol ethoxylate, oleyl alcohol ethoxylate, nonylphenol ethoxylate, p-dodecanol, oleyl alcohol.

To obtain copolymers according to this invention, a two-stage process of either direct esterification of diacids and diols, or transesterification of diesters and diols, followed by a polycondensation reaction under reduced pressure is usually used.

A suitable method for preparing copolymers according to the present invention includes heating the corresponding starting compounds for segments (i)-(im) with the addition of a catalyst to a temperature of 160-2207"C, preferably starting at atmospheric pressure, and then continuing the reaction under reduced pressure at a temperature of 160-24076 .

Reduced pressure preferably means a pressure of 0.1-900 mbar and more preferably a pressure of 0.5-500 mbar.

Conventional transesterification and condensation catalysts known in the art can be used to prepare copolymers, such as catalysts based on antimony, germanium, and titanium. Preferably, tetraisopropyl orthotitanate (IRT) and sodium acetate (MAODS) are used as a catalytic system in the method.

Additionally, this invention provides a method for creating an active oxygen barrier in a plastic packaging material, which includes incorporating an effective amount of a simple polyester-polyether copolymer and a transition metal catalyst into a thermoplastic polymer material, which is preferably a polyester, polyolefin, polyolefin copolymer, or polystyrene

Accordingly, another object of the present invention is an active oxygen barrier composition that contains a simple polyester-polyether copolymer, as described above, and a catalyst based on a transition metal, preferably with a concentration of 0.001-595 wt., more preferably 0.01 -0.595 relative to the total mass of the oxygen barrier composition.

Without being bound by any theory, it is believed that the polyester-polyester copolymer is an oxidizing substrate in which the end groups at the ends of the chains are able to control the penetration of oxygen and form a controlled active oxygen barrier.

The speed of the oxygen absorption reaction can be changed by the number and chemical composition of the end groups.

A transition metal catalyst also initiates and accelerates the rate of oxygen absorption. The mechanism by which this transition metal functions is not defined.

The catalyst may or may not be consumed with oxygen or, if consumed, may be consumed only temporarily by reverse conversion to the catalytically active state.

More preferably, the transition metal-based catalyst is in the form of a salt, and the transition metal is selected from the first, second, or third transition series of the Periodic Table of Elements. Suitable metals and their oxidation states include, but are not limited to, manganese ІІ or ІІ, iron ІІ or І, cobalt ІІ or І, nickel ІІ or ІІ, copper ІІ or ІІ, rhodium ІІ,

And or IM and ruthenium. The degree of oxidation of the metal upon introduction does not necessarily have to correspond to the state of the active form. The metal is mainly iron, nickel, manganese, cobalt or copper; more preferably manganese or cobalt; and even more preferably cobalt. Suitable metal counterions include, but are not limited to, chloride, acetate, acetylacetonate, propionate, oleate, stearate, palmitate, 2-ethylhexanoate, octanoate, neodecanoate, or naphthenate.

A metal salt can also be an ionomer, in which case a polymeric counterion is used. Such ionometers are well known in the art.

Even more preferably, the salt, transition metal, and counterion either meet the country's regulations for food contact materials or, if part of the packaging product, essentially prevent migration from the permeation barrier composition.

From oxygen, to the contents of the package. Particularly preferred salts include cobalt oleate, cobalt propionate, cobalt stearate and cobalt neodecanoate.

Another object of the invention is a plastic material that contains: component a), which is a thermoplastic polymer, preferably selected from the group consisting of complex polyesters, polyolefins, polyolefin copolymers and polystyrenes; component b), which is a simple polyester-polyether copolymer, as described above; and component c), which represents a catalyst based on a transition metal, as described above.

The plastic material can be a concentrate, a compound, or a molded product.

Depending on its use, the plastic material may contain component B) in the amount of 0.5-99.99595 wt. or more preferably 1-99.895 wt., and component c), in the form of a concentration of a transition metal element, in the amount of 0.001-595 wt. or more preferably 0.002-495 wt. relative to the total weight of the plastic material.

Preferred components a) according to the content of the invention are polyesters. The values of the characteristic viscosity of complex polyesters are given in units of dl/g, calculated from the characteristic viscosity measured at 25"C in 60/40 wt./wt. phenol/tetrachloroethane.

The characteristic viscosity of complex polyesters is preferably in the range of about 0.55-1.14 dl/g.

Preferred polyesters are those obtained by the condensation reaction of dibasic acids and glycols.

Typically, the dibasic acid contains an aromatic dibasic acid or an ester or anhydride thereof and is selected from the group consisting of isophthalic acid, terephthalic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, diphenoxyethane-4 4"-dicarboxylic acid, diphenyl-4 4"dicarboxylic acid, 2,5-furandicarboxylic acid and their mixtures. The dibasic acid can also be an aliphatic dibasic acid or anhydride, such as adipic acid, sebacic acid, decane-1,10-dicarboxylic acid, fumaric acid, succinic anhydride, succinic acid, cyclohexanediacetic acid, glutaric acid, azelaic acid, and mixtures thereof. Other aromatic and aliphatic dibasic acids known to those skilled in the art may also be used. More than 60 preferably, the dibasic acid contains an aromatic dibasic acid, optionally additionally including up to about 2095 wt. component of the dibasic acid of aliphatic dibasic acid.

Preferably, the glycol or diol component of the complex polyester is selected from the group consisting of Kk! ethylene glycol, propylene glycol, butane-1,4-diol, diethylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, polytetramethylene glycol, 1,6-hexylene glycol, pentane-1,5-diol, 3-methylpentanediol (2,4), 2-methylpentane-( 1,4)-diol, 2,2,4-trimethylpentane-(1,3)diol, 2-ethylhexane-(1,3)diol, 2,2-diethylpropane(1,3)-diol, hexane(1, 3)-diol, 1,4-di-(hydroxyethoxy)benzene, 2,2-bis-(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis -(3-hydroxyethoxyphenyl)propane, 2,2-bis-(4-hydroxypropoxyphenyl)propane, 1,4-dihydroxymethylcyclohexane and their mixtures. Additional glycols, known to specialists in this field of technology, can also be used as a glycolic component of a complex polyester.

The two preferred polyesters are polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). PET and PEN may be homopolymers or copolymers that additionally contain up to 10 mole percent of a dibasic acid other than terephthalic acid or naphthalene dicarboxylic acid and/or up to 10 mole percent of a glycol other than ethylene glycol.

PEN is preferably selected from the group consisting of polyethylene naphthalene 2,6-dicarboxylate, polyethylene naphthalene-1,4-dicarboxylate, polyethylene naphthalene-1,6-dicarboxylate, polyethylene naphthalene-1,8-dicarboxylate and polyethylene naphthalene-2, 3-dicarboxylate. More preferably, PEN represents polyethylene naphthalene-2,3Z-dicarboxylate.

More preferably, the plastic material is selected from the group consisting of PET, for example, starting PET for bottles and PET waste (PC-PET), cyclohexanedimethanol/PET copolymer (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PB) and mixtures thereof.

Also preferred plastic materials are bio-based polymers, preferably polyethylene furanoate (PEP), as well as biodegradable complex polyester, preferably selected from the group consisting of Polylactic Acids, polycaprolactones (PSI) and polyhydroxybutyrates (PHB); and bio-based polyesters derived from renewable resources such as corn and sugar cane and by-products associated with their harvesting and

Co.) processing, but are not biodegradable.

Preferred polyolefins and polyolefin copolymers, i.e. component a) in the meaning of the invention, are thermoplastic polyolefins known in the art and are selected from the group consisting of - polyethylene (PE), preferably selected from the group consisting of high density polyethylene ( HOPE), medium density polyethylene (MOPE), low density polyethylene (HOPE), linear low density polyethylene (HOPE), metallocene low density polyethylene (th OPE) and metallocene linear low density polyethylene (th HOPE), - polypropylene (PP), preferably selected from the group consisting of polypropylene homopolymer (PPH), propylene statistical copolymer (PP-K) and propylene block copolymers (PP-BiosKk-SORO), - PE copolymers, preferably selected from the group consisting of ethylene vinyl acetate copolymers ( EMA), ethylene and methyl acrylate copolymers (EMA), ethylene and butyl acrylate copolymers (EVA), ethylene and ethyl acrylate copolymers (EEA) and cycloolefin copolymers (SOS), - general-purpose polystyrene (SRRP) and impact-resistant polystyrene (RIRP); more preferably - high-density polyethylene (HOPE) and low-density polyethylene (HOPE), - polypropylene homopolymer (PPH), - general purpose polystyrene (GPP).

Preferable polystyrenes, that is, component a) according to the content of the invention, can be a homopolymer of styrene, a homopolymer of alkylstyrene, preferably a homopolymer of C1-Ca4 alkylstyrene, for example, a homopolymer of amethylstyrene; styrene copolymer, in particular impact-resistant polystyrene (NIRB).

Impact-resistant polystyrenes (NIP5) are usually obtained by graft polymerization of mixtures of styrene and optionally one or more copolymerized vinyl monomers, preferably mixtures of styrene, methylstyrene, ethylstyrene, butylstyrene, halostyrenes, vinylalkylbenzenes, such as vinyltoluene, vinylxylene, acrylonitrile, methacrylonitrile, lower alkyl methacrylic acid esters in the presence of an elastic polymeric main chain, which includes copolymers selected from polybutadiene, polyisoprene, rubber-like bostyrenediene copolymers, acrylic rubber, nitrile rubber and olefin rubbers,

such as propylene monomer rubber (ROM) and propylene rubber (PC). In impact-resistant polystyrene, the elastic polymer main chain is usually 5-8095 wt., preferably 5-5095 wt. From the total weight of grafted polymer.

Optionally, the composition of the active oxygen barrier and the plastic material of the present invention contain one or more additional substances (component 4), which are selected from the group consisting of - natural dyes obtained from plants or animals, and synthetic dyes, preferably synthetic dyes are synthetic organic and inorganic dyes and pigments, - preferred synthetic organic pigments are azo- or disazo pigments, lacquer azo- or disazo pigments or polycyclic pigments, more preferably phthalocyanine, diketopyrrolopyrrole, quinacridone, perylene, dioxazin, anthraquinone, thioindigo, diaryl or quinophthalone pigments ; - the predominant synthetic inorganic pigments are metal oxides, mixed oxides, aluminum sulfates, chromates, metal powders, mother-of-pearl pigments (mica), fluorescent paints, titanium oxides, pigments based on cadmium and lead, iron oxides, carbon black, silicates, nickel titanates, pigments based on cobalt or chromium oxides; - surfactants; excipients, preferably acid scavengers, process additives, binding agents, lubricants, stearates, foaming agents, polyhydric alcohols, nucleating agents or antioxidants, for example stearates or oxides such as magnesium oxide; - antioxidants, mainly primary or secondary antioxidants; - antistatic; - compatibilizers for polyester/polyamide mixtures; - UV absorbers, additives that reduce friction, anti-fogging agents, anti-condensation agents, suspension stabilizers, anti-caking agents, waxes and mixtures of these substances.

More preferably, component 4) is selected from the group consisting of compatibilizers, UV absorbers, antioxidants and dyes.

Component 4) can be present in an amount of 0-6095 wt., preferably 0.001-5095 wt., more preferably 0.1-3095 wt., most preferably 1-2595 wt., relative to the total weight of the plastic material.

It is expedient to mold the plastic material according to this invention into a plastic product, for example, by blow molding.

Accordingly, another object of the present invention is a molded plastic product that includes the specified plastic material.

The molded plastic product according to the invention can be a packaging material, preferably a container, film or sheet, especially for use in the packaging of personal care products, cosmetics, household, industrial, food products and beverages, where a high oxygen barrier is required.

Packaging materials can be flexible, rigid, semi-rigid or combinations thereof. Rigid packaging products usually have a wall thickness of 100-1000 micrometers.

Conventional flexible packages are usually 5-250 micrometers thick.

Rigid packaging products or flexible films according to the invention may consist of one layer or may contain several layers.

When the packaging product or film contains an oxygen-absorbing layer, they may additionally include one or more additional layers that include an oxygen barrier or an oxygen-permeable layer. Other additional layers, such as adhesive layers, can also be used in a multilayer packaging product or film.

Another object of the invention is a method of manufacturing a plastic product, as defined above, which is characterized by the fact that the components a), b), c) and optionally a) are physically mixed with each other and subjected to the molding process.

For physical mixing, a mixing device common in the plastics industry can be used. Preferably, the mixing device may be that used to prepare a liquid concentrate or a solid concentrate, or may be a combination of these devices.

The mixing device for the liquid concentrate can be a high-speed disperser (for example, the Sou/Lez"M type), a mill, a three-roll mill, an auxiliary mill, or a rotor-stator disperser.

The mixing device used for the production of solid MB concentrates or CO compounds can be a mixer, an extruder, a kneader, a press, a mill, a calender, a blender, a casting machine, a machine for injection molding with blowing and extraction (IZVM), because the machine for extrusion with blowing (EVM), compression molding machine, compression blowing machine; more preferred mixer, extruder, injection machine, injection and extrusion machine, injection molding machine; even more preferably a mixer, an extruder, a blow and pull injection molding machine, and a blow extrusion machine.

The process of product formation depends on the desired shape of the manufactured product.

Containers are mainly made by blow molding, injection molding, blow molding, blow extrusion, blow molding, blow molding, and blow molding.

Films and sheets are preferably produced using casting or blow extrusion or co-extrusion processes, depending on the required thickness and number of layers required to achieve certain properties, which are ultimately followed by post-extrusion forming processes such as thermoforming or stretching . In the process of thermoforming, a plastic sheet is heated to the appropriate forming temperature, formed into a given shape in a mold and cut to create the final product. If a vacuum is used, the process is usually called vacuum forming. In post-extrusion drawing processes, the extruded film can be, for example, oriented in two directions by drawing. All of the above processes are well known in the art.

Mixing of components can take place in one stage, in two stages or in several stages.

Mixing can take place in one stage, when components a), B), c) and optionally component 4) or only B), c) and optionally component a) are directly dosed and/or introduced in the form of liquid or solid concentrates or as pure components, such as in a blow and pull injection molding machine.

Mixing can also take place in two or three stages, and in the first stage components B), c) and optionally 4) are pre-dispersed in component a), and in one or more successive stages are added to component a).

Mixing can also take place in two or three stages, and in the first stage, components c) and optionally component 4) are pre-dispersed in component a), and component B) is directly dosed and/or introduced as a pure component, for example, in

A blow and pull injection molding machine.

Preferably, component B) and component c) are pre-dispersed in component a) to form two separate concentrates and then these concentrates are combined with components a) and optionally 4). In one preferred embodiment, in the first stage, component B) and optionally component 4) are dispersed in component a), while component c) is dispersed in component a) to obtain two separate concentrates. After compounding in the melt, for example, in a single-screw or twin-screw extruder, the extrudates are obtained in the form of strands and extruded in the form of tablets according to conventional methods, such as cutting.

In the second stage, the resulting concentrates are dosed and fed by a converter/compounder into the main stream of component A granules, for example, in a blow and pull injection molding machine. These extrudates can be dosed and introduced into the main flow of component a) directly into the injection process, avoiding the mixing process.

In another implementation, at the first stage, components B), c) and optionally component 4) are dispersed in component a) to obtain a concentrate. After compounding in the melt, for example, in a single-screw or twin-screw extruder, the extrudate is obtained in the form of strands and extruded in the form of tablets according to conventional methods, such as cutting. In the second stage, the obtained solid concentrate is dosed and fed by a converter/compounder into the main stream of component a, for example, into a blow and pull injection molding machine at a speed corresponding to the required final concentration of components B) and c) in the product.

Mixing preferably occurs continuously or periodically, more preferably continuously; in the case of a solid MV concentrate preferably by extrusion, mixing, grinding or calendering, more preferably by extrusion; in the case of liquid MV concentrate, preferably by mixing or grinding; in the case of connecting CO, preferably by extrusion or calendering, more preferably by extrusion.

Mixing is preferably carried out at a temperature of 0-33070.

The mixing time is preferably from 5 s to 36 h, preferably from 5 s to 24 h.

The mixing time in the case of continuous mixing is preferably from 5 seconds to 1 hour.

The mixing time in the case of periodic mixing is preferably from 1 to 36 hours.

In the case of liquid MV concentrate, mixing is preferably carried out at a temperature of 0-150 60 "C with a mixing time of 0.5-60 minutes.

In the case of a solid MB concentrate or a CO compound, mixing is preferably carried out at a temperature of 80-330 "C with a mixing time of 5 seconds to 1 hour.

Specific products according to the present invention include preforms, containers, films and sheets for packaging food products, beverages, cosmetics and personal care products where a high oxygen barrier is required. Examples of beverage containers are: bottles for juice, sports drinks, beer or any other beverage in which oxygen adversely affects the taste, aroma, characteristics (prevents degradation of vitamins) or color of the beverage. The compositions according to the present invention are also particularly useful as a sheet for thermoforming into rigid packages and films for flexible structures. Hard bags include food trays and lids. Examples of food tray applications include heat-resistant food trays or cold storage trays, both in the main container and in the lid (whether a thermoformed lid or film), in which the freshness of the food contents may deteriorate when exposed to oxygen.

Preferred products of this invention are rigid packaging products such as bottles and thermoformed sheets and flexible films.

An additional aspect of the present invention relates to single-layer films. The term "single-layer film or monolayer cast film or single-layer sheet" refers to a semi-finished product consisting of a sheet (blank), usually obtained by extruding films that form a layer. The resulting sheet was not subjected to the process of preferential orientation and is therefore not oriented.

The sheet may subsequently be transformed into a finished product such as a container by known processes that do not require orientation, usually by thermoforming. The term "container" refers to any product that has an opening for the introduction of a product, in particular food products.

To determine the ability to absorb oxygen of the copolymers according to the invention, the rate of oxygen absorption can be calculated by measuring the time that has passed until a certain decrease in the oxygen content in the sealed container.

Another definition of acceptable oxygen absorption comes from testing real packages.

The ability to absorb oxygen by the product according to the invention can be measured by determining the amount of oxygen consumed before the absorption efficiency of the product is exhausted.

The plastic material of this invention offers an oxygen absorption system with high oxygen absorption capacity, precise adjustment of the oxygen transmission rate into the interior of the package, and suitable transparency of the final plastic products.

Test methods

Product properties are determined by the following methods, unless otherwise indicated:

The density value is determined in accordance with the document AZTM 0792 (g/cm3).

The value of the melt flow rate (MEK) is determined in accordance with the document ATM 01238 (G/10 min at the specified temperature and mass).

The method of measuring the absorption capacity of oxygen

The cast film, which includes the appropriate absorbent composition, is introduced into a glass vessel equipped with an optical sensor and a rubber cover.

Measurement of the oxygen content in the free space of the vessel is further carried out using two different methods. One of them is a non-permeable measurement with an oxygen sensor and transducer

EirokhF). Another is SpeskMaie Z Ог (71) СО2-10095.

For both of them, data is collected in parallel, for at least two samples of the same composition at regular intervals. For each sample, the oxygen uptake at a given time is calculated as the difference between the oxygen content measured at the current time and the oxygen content measured at time 0, which is close to 2195. The oxygen uptake is then averaged over the number of samples measured for each composition, and applied depending on time.

Implementation of the invention

Examples by mass, indicated in the following examples, are given relative to the total mass of the mixture, composition or product; parts are mass parts; "eh" means an example; "seh" means a comparative example; MV means concentrate; CO means connection, "O" means direct dosing of the corresponding additives.

Used equipment

Equipment used to perform industrial tests of cast film

PET, described below, consists of - a single-layer extruder, screw diameter 25 mm - 1 filter changer with a filter mesh of 40 μm bo - 1 forming flat head with a width of 350 mm for the production of a single-layer film

- 1 horizontal calender with Z rollers

Substances used

Component a: A1:

Polyethylene terephthalate (PET), which has a density of 1.35-1.45 g/cm and a characteristic viscosity of 0.74-0.78 dl/g (ATM 03236-88).

Component a: Ag:

Polybutylene terephthalate (PBT), which has a density of 1.28-1.32 g/cm3 and a characteristic viscosity of 0.90-1.00 dl/g (ATM 03236-88).

Component B: B1-B13:

Complex polyester-simple ethers are prepared using the following general technique:

In a 500 ml multi-mouthed flask equipped with a KRO stirrer, a Herringbone dephlegmator, a vacuum source and a nozzle, chemicals according to Table 1 are placed in the reactor under a nitrogen atmosphere and in the amount indicated in Table 1. The mixture is heated to an internal temperature of 60 "C with subsequent addition of 200 μl of tetraisopropyl orthotitanate.

During 2 hours, the temperature of the reaction mixture is continuously raised to 2307C with a weak nitrogen flow (5 l/h) and maintained at this temperature for 2 hours. After reaching 70 "C, methanol begins to evaporate. After reaching 1907, ethylene glycol begins to continuously evaporate. After that, the flow of Mo is stopped and the pressure of the reaction mixture is continuously reduced to 400 mbar at 230 "C for 165 minutes, followed by a continuous decrease in pressure to 1 mbar for 90 minutes. At the next stage, the reaction mixture is stirred at a pressure of 1 mbar and an internal temperature of 2307C for an additional 4 hours. After this period of time, the internal pressure in the reaction flask is again brought to 1 bar, using

Me, and then the polymer melt is removed from the reactor and allowed to solidify.

To determine the molecular weight of a complex polyester-simple ether, measurements are carried out using GPC under the following conditions

Columns: 1 x RU5 BOM Spaga, 5 μm, 50 mm x 8.0 mm IU 1 x RUB BOM 100 A, 5 μm, 300 mm x 8.0 mm IU 1 x RUB BOM 1000 A, 5 μm, 300 mm x 8.0 mm IU 1 x RUB BOM 100000 A, 5 μm, 300 mm x 8.0 mm IU

Zo Detector: CI

Furnace temperature: 407

Consumption: 1 ml/min.

Injection volume: 50 μl

Eluent: THF

Calculation of RZZ-MpORS Version 8.2

Calibration: polystyrene standards in the 682-1,670,000 dalton range

Internal standard: toluene

Injection concentration: 4 g/L THF

Table 1

Roiu- | Roiu- | READY| rv- 2 schi ma-

Zra- | OMT/ TNE | TNE MREV | MA | Karo- We | MM" she

In 14851 | Ш|500Ш1250| /|2501| | | (1,250!

And with 14851 | Sh|5001438| /|63| | | (1250! |03 |02Ш|7.51 35318 | 16430) you 14851 6 yu | Sh|50015001 | | | (1,250!

Vb 148.51 49 | Sh|5001438| |63| | | (1250! |03 |02|7.51 36165 | 15054) in/ 485149 /|500Щ1469| |z31 | | | 1251 |from (011751 24979 | 10948 in 14865) Sh|50ОЙ 375, |71251| | | (1,250! 51 38476 | 17954) vVi11485| | |500, | |7251| 193751 6 yush Sh|3751 2 |03(0417,51 32345 | 11953) vi21|1485| | |500Щ1375| |125| | /|253| |257 | 03 | 04 | 751 29894 | 13465

And vi314865| | |500,| | |7188| /3731 3751 |03(06Ш|1,5I| 25310 |10501) " 84 Comparative sample - no end group was used for the synthesis of this polymer

OMT « dimethyl terephthalate MREC 750 - monomethoxylated poly(ethylene glycol)-monool

OMI « dimethyl isophthalate (average molecular weight (Mp) - 0.75 kDa)

Roiu-TNE 1000 - Poly-THF-diol (average molecular weight (Mp) - 1 kDa)

M41 - Monomethoxylated poly(ethylene glycol)-co-poly(propylene glycol)-monool (average molecular weight (Mp) - 2 kDa)

Roiu-TNE 2000 - Poly-THF-diol (average molecular weight (Mp) - 2000 kDa)

ES - ethylene glycol

RES 1000 - Poly(ethylene glycol)-diol (average molecular weight (Mp) - 1 kDa)

RO - Propylene glycol

RK 1000 - poly (ethylene glycol)-co-poly(propylene glycol)-diol (average molecular weight (Mp) - 1 kDa)

Component c: C1:

Solid form of cobalt stearate (concentration of elemental cobalt 9.595).

Component 4: 01:

Surfactant

Concentrates МВ1-МВ1О0

The components are homogenized together using the 25E18HP extruder at a temperature of 260 "C to obtain a solid MV concentrate; Table 2 gives detailed information.

Table 2

JSC | Ag |V | v84 | 8588) in | in | in | v2|viz| Article | o mV 8 HER 17 HER 1 1 1 1 1 1 en 123 122311 (Compound) " " me 9 HER |0th 1 1 1 1 1 1 mV |9| HER | | ,l0 | its 1 mvB |9| HER / HER HER /yu0 her 1 mb |9| HER HER HER HER 0 mv7 | 9 HER 1 HER 1 1 1 101 mV | 9 HER HER HER 1 1 1 10 me | 9 HER 1 1 1 1 1 1 1 1 0 and mV | |86th | | / | | | / 6181

Production of cast films:

As an example of the operating mode, cast films with a thickness of 200 μm are obtained by extrusion using Soipd E 25 RK by introducing component A1, pre-dried for 18 hours at 120 "С, into the main hopper of the apparatus and by adding other components (directly dosed MV and/or pure additives) through dosing devices that are added to the main flow of the AT component before entering the cylinder of the injection unit.

The extruder temperature can be maintained at 260 "C and the flathead temperature is 270 76.

The working conditions during the test are as follows: T1 - 60 "C/12 - 240 "C/13 - 260 "C/14 - 260 "C/5 - 260 "SL of the head At 270 "C/1 of calenders At 70 "C/ revolutions screw 80 rpm.

Table Z оежсрех | Type material | Composition() -:/ пит З МИ ПНЯ ПОН ТОЛИ те ОО НО еЗз | 60 g 2 e4 | 0 g pyt: p po zo NAD o srehb// | 0 F 1.7 MVI1O 78.3 RET i

The oxygen absorption capacity (in ml OO: per gram of the composition), which corresponds to cast films, is measured by the methods described above. Table 4 shows data on oxygen absorption by compositions with different copolymer structures and different number of end groups.

Table 4 00 | 02 | 04 | 08 | 04 | 06 in srehb eh5 eh | 0000000Yi eh eh13

Day: | shea 770 1 00 1 00 1 00 | 00 | 00 | 00 772 | 62 | 62 1 47 | 20 81Г1111117111111111171108 106 776 1 240 | 208 | 179 | 64 779.1 375 | For 1 274 | 928 0 Г111111111111111130 1165 712.1 447 1 422 | 360 | 71718 27 1111111111111111394 | 197 19 .| 6853 | 644 | 556 | 230 7723 | 768 2 |Dr7b5 1645 | 314 | | sh( 7.26... | 822 | 765 | 681 | 369 728 | 918 2 sh| 7858 | 76 | 409

When comparing ex3, ex4, ex5 and srehb, a significant dependence of the oxygen absorption rate on the number of end groups present is observed. Generally, the amount of oxygen absorbed decreases when more groups are introduced. The rate of oxygen absorption depends significantly on the number of end groups contained in complex polyester - co-simple polyester, therefore, the amount of absorbed oxygen can be accurately adjusted and controlled by increasing or decreasing the number of end groups.

This effect is observed when additives of complex polyester - copolyether are dosed together with the resin directly into the loading mechanism of the extruder, as well as during the preparation of MV.

EX11 and EX13, which refer to complex polyesters with end groups that differ from polyesters EX3-EX5 and srehb, show exactly the same behavior: higher amounts of end groups reflect a decrease in oxygen absorption.

Claims (15)

FORMULA OF THE INVENTION 1. Simple polyester-complex polyester copolymer, which includes: () segments of simple polyester, in which at least one segment of simple polyester contains at least one segment of polytetramethylene oxide; (i) segments of complex polyester; (ii) bridging elements of the structure-"СОН2СО-", in which K2 is, optionally, a substituted divalent hydrocarbon residue consisting of 1-100 carbon atoms; (m) one or two terminal groups K1-0-(02-04-0-)6e-7, where K1 is, optionally, a substituted hydrocarbon residue and e is an integer from 0 to 1000. 2. A simple polyester-complex polyester copolymer according to claim 1, in which the segments of the simple polyester Zo (i) contain segments of ethylene oxide, segments of propylene oxide or their combination. 3. Simple polyester-complex polyester copolymer according to claim 1 or claim 2, in which segments of the complex polyester (ii) are represented by formula (II): yazi-o- (1) in which " represents a bond with a bridging element (her), K2 and KZ independently of each other represent, optionally, a substituted hydrocarbon residue consisting of 1-100 carbon atoms, and y is an integer of 1-50. 4. A simple polyester-polyether copolymer according to any of the previous claims 1-3, in which the bridging elements are described by the formula (PP): o d) And in which K2 is, optionally, a substituted hydrocarbon residue consisting of 1-100 carbon atoms. 5. A simple polyester-polyester copolymer according to any of the previous claims 1-4, in which the end groups are described by the following general formula: B81-0-(С2-С4-О-)е-7, in which КИ! represents an aliphatic hydrocarbon residue with 1-24 carbon atoms, an olefinic hydrocarbon residue with 2-24 carbon atoms, an aromatic hydrocarbon residue with 6-14 carbon atoms, and the indicated hydrocarbon residues are optionally substituted C1-Cv- alkoxy, nitro, cyano , sulfo or a combination thereof and e is an integer from 0-500. 6. Simple polyester-complex polyester copolymer according to any of the preceding claims 1-5, in which B81-(Сб2-04-0-)е-" corresponds to the following formulas: - sn, ve DA and t You o-yiv » o-is- sn, g tut MAK KI Os a Oo--if" shchi v o-te 5 o-i-x sn, r v o-a : o- в» СН» в а Adtityao А ОИЙ с о я" сн, in which different monomers are distributed randomly, in blocks or a combination of random and block distribution, and p is an integer 0-250, and is an integer 0-250, c is is an integer 0-70, and the sum of the atrays is 0-570; and K1 is as defined in claim 5. 7. Simple polyester-polyester copolymer according to any of the previous claims 1-6, in which K1 denotes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, n-pentyl, isopentyl, t-pentyl , neopentyl, 1,2 dimethylpropyl, isoamyl, n-hexyl, utorhexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, tridecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, methylphenylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl. 8. A simple polyester-polyether copolymer according to any of the previous claims 1-7, in which the number average molecular weight is 2000-1000000 g/mol. 9. A simple polyester-polyether copolymer according to any of the previous claims 1-8, in which the mass ratio 0, which is defined as the mass ratio of the content of poly(tetramethylene oxide) to the total content of all elements of the dicarbonyl structure (ii) and (ii), is 0.1-10. 10. A simple polyester-polyester copolymer according to any of the previous claims 1-9, in which the mass ratio О, which is defined as the mass ratio of the content of the end group to the total content of all elements of the dicarbonyl structure (ii) and (ii), is between 0.001 of 100. 11. The method of obtaining a simple polyester-complex polyester copolymer according to any of the preceding claims 1-10, which includes polycondensation of simple polyester segments containing at least one polytetramethylene oxide segment, complex polyester segments, bridging elements and end groups. 12. Active oxygen barrier composition, which includes a simple polyester-polyether copolymer according to claims 1-10 and a catalyst based on a transition metal. 13. Plastic material that contains: component a), which is a thermoplastic polymer; component B), which is a simple polyester-polyester copolymer according to any of claims 1-10; and component c), which is a catalyst based on a transition metal. 14. Plastic material according to claim 13, which is a concentrate, compound or molded product. 15. Plastic material according to claim 13 or 14, which is a container or a film or a part thereof.